WO1994004741A1 - Washing process - Google Patents

Washing process Download PDF

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Publication number
WO1994004741A1
WO1994004741A1 PCT/EP1993/002170 EP9302170W WO9404741A1 WO 1994004741 A1 WO1994004741 A1 WO 1994004741A1 EP 9302170 W EP9302170 W EP 9302170W WO 9404741 A1 WO9404741 A1 WO 9404741A1
Authority
WO
WIPO (PCT)
Prior art keywords
detergent
washing
sugar
wash liquor
concentration
Prior art date
Application number
PCT/EP1993/002170
Other languages
German (de)
French (fr)
Inventor
Werner Kuhlmann
Hans-Willi Kling
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to US08/392,757 priority Critical patent/US5498546A/en
Priority to JP6505885A priority patent/JPH08500439A/en
Priority to EP93919061A priority patent/EP0656081B1/en
Priority to DE59304835T priority patent/DE59304835D1/en
Publication of WO1994004741A1 publication Critical patent/WO1994004741A1/en

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/11—Automated chemical analysis
    • Y10T436/117497—Automated chemical analysis with a continuously flowing sample or carrier stream
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/12—Condition responsive control
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/25—Chemistry: analytical and immunological testing including sample preparation
    • Y10T436/25125—Digestion or removing interfering materials

Definitions

  • the present invention relates to a washing method in which the concentration of the wash liquor is determined analytically.
  • the invention relates to a washing process using an aqueous solution of detergent active substance, in which the concentration of detergent active substance in the solution is determined indirectly by determining the content of a reducing sugar in the preparation of the wash liquor is added in an amount proportional to the amount of detergent active.
  • the sugar has preferably been mixed in a certain constant ratio of the detergent substance or the mixture of several detergent substances, also referred to as detergent, before the actual wash liquor is prepared.
  • Detergent substances in the sense of the present application are primarily surfactants and builder substances, but also, for example, graying inhibitors, bleaching agents, enzymes, detergency boosters and antimicrobial agents.
  • Glucose is preferably used as the reducing sugar.
  • reducing sugars as tracer substances not only solves the problems of the previously known concentration determination methods because these compounds are not introduced into the wash liquor in any significant amounts or are absorbed on textile fibers, but also offers unexpected advantages in the analysis itself it has been found that these compounds can be determined virtually undisturbed by the other detergent ingredients in the solution and that this determination can also be carried out so quickly that their result can be used to control ongoing processes.
  • sugars are biodegradable and toxicologically safe and do not interfere with the washing process.
  • the amount of sugar that must be added to the wash liquor depends primarily on the sensitivity with which the compound used can be determined analytically under these conditions. Of course, the amount to be selected also depends to a large extent on the analytical method.
  • the use concentrations are usually between about 0.02 to 2 g / 1 wash liquor, preferably between about 0.1 and about 1 g / 1 wash liquor. If the reducing sugars are incorporated directly into the detergent from which the wash liquor is produced, these detergents contain, in addition to at least one surfactant and at least one builder substance, about 1 to 20% by weight, preferably 3 to 10% by weight, of reducing sugar . If the wash liquor is not produced from a detergent which contains all the components necessary for washing, the liquor is prepared by adding individual active ingredients or combinations of active ingredients, to which the reducing sugar is added beforehand, they accordingly contain more reducing sugar.
  • the analytical method with the aid of which the sugar content in the wash liquor is determined, can be freely selected within almost any limits and adapted to the conditions of the washing process. Sensitive determination methods which allow low sugar contents to be used and methods which allow rapid determination in a continuous manner are preferred.
  • the photometric determination of the sugar content after an upstream color-forming reaction between the tracer and an added reagent is therefore particularly preferred.
  • the coloring reaction can be carried out on individual samples of the wash liquor to be analyzed and then leads to corresponding individual results according to photometry. For continuous concentration monitoring, however, there is also the possibility of carrying out the reaction between tracer and reagent continuously in a stream branched off from the wash liquor, the process of flow injection analysis having proven particularly useful.
  • an equivalent stream of one or more reagents is metered into the branched-off stream of the solution to be analyzed, if appropriate after suitable pretreatment, such as filtration or tempering, and the common stream then, after appropriate mixing, if necessary, further measures such as heating, continuously exposed until the desired color reaction has taken place and the solution can be fed to a photometric measuring cell.
  • suitable pretreatment such as filtration or tempering
  • further measures such as heating
  • Typical flows for the solutions range from 0.1 to 2.5 ml per minute.
  • aromatic hydrazine compounds for example 4-aminobenzhydrazide
  • these aromatic hydrazine compounds form, together with the reducing sugars, in particular glucose, intensely yellow-colored hydrazones which can be easily detected photometrically.
  • This reaction is known from the literature for the analytical detection of sugars, so that a more detailed description of the reaction conditions can be dispensed with here. It is noteworthy that this coloring reaction of the sugar takes place largely independently of other constituents of the detergent.
  • the process according to the invention can advantageously be used wherever the content of active substance in a wash liquor has to be determined subsequently. This is particularly the case in the commercial area of the laundry, where one and the same wash liquor is often used for several washing processes and in the course of which by various influences, for example by adding more dilute liquors or water or by discharging the concentrated liquor the laundry can be depleted of washing active substance in an uncontrolled manner.
  • the current content of active substance can first be determined using the method according to the invention and then detergent can be added according to the result. Since the method according to the invention can be carried out largely to completely automatically, it is particularly suitable for the more or less automatic control of this detergent dosing, which is sought today in the production or regeneration of washing liquors in commercial laundries.
  • the powder detergent used contained silicate and soda as builder substances and alkylbenzenesulfonate, fatty alcohol ethoxylate and soap as surfactants and 5.00% by weight glucose as tracer substance.
  • the detergent concentration in the liquor was recorded in chamber 1 and in chamber 5 via a bypass control and the analysis method according to the invention and controlled by means of a microprocessor by comparing the programmed target values with the actual values found.
  • the equipment used for the analysis was composed of standard building blocks, which were diameter 0.5 mm) had been connected.
  • the following solutions were used:
  • Solution 1 2.5 g of 4-aminobenzhydrazide and 12 g of NaOH in 150 ml of water
  • Solution 2 Commercial buffer solution pH 4.62 (acetate buffer) diluted with the same volume of water
  • Both solutions were fed separately via pumps at 1 ml / minute and fed to a mixing section via a T-piece.
  • samples 1 of the washing liquor in each case 20 .mu.l
  • samples 1 of the washing liquor were supplied in segmented form to solution 1 using a metering valve and a metering loop.
  • the liquid stream was heated to 70 ° C. in a temperature control section.
  • the extinction of the liquid was determined continuously at 410 nanometers. The maximum values of the extinction were regarded as a measure of the glucose concentration and as such were continuously processed by a connected computer.
  • the calibration was carried out with the aid of aqueous glucose solutions in the concentration range between 0.02 and 0.3 g glucose per liter, which were fed into the analysis circuit instead of the wash liquor several times a day.
  • the sensitivity was automatically corrected by the computer. A correction to eliminate the self-extinction of the glucose-free wash liquor was not necessary in the present case.
  • the analysis values determined by the computer were compared by a microprocessor with the target values programmed in there, which in turn actuated the metering valves of the individual chambers and, if necessary, caused the detergent to be replenished in an appropriate amount.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • Biophysics (AREA)
  • Molecular Biology (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
  • Detergent Compositions (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

The invention relates to a washing process known per se in which the detergent concentration is analytically determined indirectly by determining the content of a reducing sugar which, when the detergent is prepared, is added in a quantity which is proportional to that of the active washing substance. To this end the sugar may be added before the preparation of the actual detergent in a given constant ratio to the active washing substance or the washing agent to be used.

Description

"Waschverfahren" "Washing process"
Die vorliegende Erfindung betrifft ein Waschverfahren, bei dem die Konzentration der Waschlauge analytisch bestimmt wird.The present invention relates to a washing method in which the concentration of the wash liquor is determined analytically.
Beim maschinellen Waschen von Textilien besteht vor allem im ge¬ werblichen Bereich der Wunsch, die Dosierung des Waschmittels bei der Herstellung oder Regenerierung der Waschlauge teilweise oder vollständig automatisch ablaufen zu lassen. Für eine bedarfsge¬ rechte Steuerung dieser Dosierung hat es sich als zweckmäßig er¬ wiesen, nicht nur externe Vorgaben, sondern auch die tatsächliche Konzentration an Waschaktivsubstanz in der Lauge als Richtgröße für die weitere Dosierung heranzuziehen. Die notwendige Dosierung ergibt sich dann aus der Differenz zwischen Soll und Ist-Wert der Konzentration an Waschaktivsubstanz. Man verwendet derartige Steuerungsprozesse heute in erster Linie in kontinuierlich arbei¬ tenden Waschstraßen, wobei man zur Bestimmung des Gehaltes an Waschaktivsubstanz in der Flotte die Tatsache ausnützt, daß mit steigender Konzentration die Gesamtleitfähigkeit der Flotte an¬ steigt. Der Zusammenhang zwischen Leitfähigkeit und Konzentration an Waschaktivsubstanzen muß für jede neue Zusammensetzung eines Waschmittels empirisch festgestellt werden. Schwierigkeiten erge¬ ben sich bei diesem System aus dem sehr stark schwankenden Eintrag von Elektrolyten mit der verschmutzten Wäsche, der zu falschen Analysenergebnissen und damit auch zu fehlerhaften Dosierungen führt. Weiterhin ist aus der Deutschen Offenlegungsschrift 29 49 254 ein Verfahren bekannt, bei dem die Konzentration von Wasch- und Reinigungsflotten photometrisch über den Gehalt an fluoreszie¬ renden Farbstoffen bestimmt wird. Nachteilig an diesem Verfahren ist die Tendenz aller Farbstoffe, sich aus Lösung an Textilfasern zu adsorbieren, so daß die Waschlauge an diesen Farbstoffen schneller als an den übrigen Wirkstoffen verarmt. Da die Adsorp¬ tion zudem auch von der Qualität des Fasermaterials abhängt, ist auf diesem Wege eine verläßliche Konzentrationsbestimmung von Waschaktivsubstanzen nicht möglich. Für eine zuverlässigere Dosie¬ rung des Waschmittels wird deshalb seit längerem nach einem Ver¬ fahren gesucht, daß unabhängig von derartigen Störeinflüssen ist.When washing textiles by machine, there is a desire, particularly in the commercial sector, to let the detergent dosage run partially or completely automatically during the production or regeneration of the wash liquor. In order to control this dosage as required, it has proven to be expedient not only to use external specifications, but also the actual concentration of detergent substance in the alkali as a guide for the further dosage. The necessary dosage then results from the difference between the target and the actual value of the concentration of detergent. Such control processes are used today primarily in continuously operating car washes, whereby the fact that the total conductivity of the liquor increases with increasing concentration is used to determine the content of detergent active in the liquor. The relationship between conductivity and concentration of detergent substances must be determined empirically for each new composition of a detergent. Difficulties arise in this system from the very fluctuating input of electrolytes with the soiled laundry, the incorrect analysis results and thus also incorrect dosages leads. Furthermore, a method is known from German Offenlegungsschrift 29 49 254 in which the concentration of washing and cleaning liquors is determined photometrically via the content of fluorescent dyes. A disadvantage of this process is the tendency of all dyes to adsorb onto textile fibers from solution, so that the wash liquor is depleted more quickly from these dyes than from the other active ingredients. Since the adsorption also depends on the quality of the fiber material, a reliable determination of the concentration of detergent substances is not possible in this way. For a more reliable dosage of the detergent, a method has therefore been sought for a long time that is independent of such interfering influences.
Ein derartig verbessertes Verfahren wurde jetzt gefunden.Such an improved method has now been found.
Gegenstand der Erfindung ist ein Waschverfahren unter Verwendung einer wäßrigen Lösung von Waschaktivsubstanz, bei dem die Konzen¬ tration an Waschaktivsubstanz in der Lösung indirekt dadurch er¬ mittelt wird, daß der Gehalt an einem reduzierenden Zucker be¬ stimmt wird, der bei der Zubereitung der Waschlauge in einer Menge zugesetzt wird, die der Menge an Waschaktivsubstanz proportional ist. Vorzugsweise ist dabei der Zucker in einem bestimmten kon¬ stanten Verhältnis der Waschaktivsubstanz oder dem Gemisch mehre¬ rer Waschaktivsubstanzen, auch als Waschmittel bezeichnet, vor der Zubereitung der eigentlichen Waschlauge zugemischt worden.The invention relates to a washing process using an aqueous solution of detergent active substance, in which the concentration of detergent active substance in the solution is determined indirectly by determining the content of a reducing sugar in the preparation of the wash liquor is added in an amount proportional to the amount of detergent active. The sugar has preferably been mixed in a certain constant ratio of the detergent substance or the mixture of several detergent substances, also referred to as detergent, before the actual wash liquor is prepared.
Als Waschaktivsubstanzen im Sinne der vorliegenden Anmeldung gel¬ ten in erster Linie Tenside und Buildersubstanzen, daneben aber auch beispielsweise Vergrauungsinhibitoren, Bleichmittel, Enzyme, Waschkraftverstärker und antimikrobielle Wirkstoffe. Als reduzierender Zucker wird vorzugsweise Glucose eingesetzt.Detergent substances in the sense of the present application are primarily surfactants and builder substances, but also, for example, graying inhibitors, bleaching agents, enzymes, detergency boosters and antimicrobial agents. Glucose is preferably used as the reducing sugar.
Die Verwendung der reduzierenden Zucker als Tracersubstanzen löst nicht nur die Probleme der bisher bekannten Konzentrationsbestim- ungsverfahren, weil diese Verbindungen weder in nennenswerten Mengen in die Waschlauge eingeschleppt werden noch auf Textilfa- sern aufziehen, sondern bietet auch unerwartete Vorteile bei der Analyse selbst. So hat sich herausgestellt, daß diese Verbindungen praktisch ungestört von den übrigen Waschmittelinhaltsstoffen in der Lösung bestimmt werden können und diese Bestimmung auch so schnell durchführbar ist, daß ihr Ergebnis zur Steuerung laufender Prozesse verwendet werden kann. Darüberhinaus sind Zucker biolo¬ gisch abbaubar und toxikologisch unbedenklich und sie stören den Waschvorgang nicht.The use of the reducing sugars as tracer substances not only solves the problems of the previously known concentration determination methods because these compounds are not introduced into the wash liquor in any significant amounts or are absorbed on textile fibers, but also offers unexpected advantages in the analysis itself it has been found that these compounds can be determined virtually undisturbed by the other detergent ingredients in the solution and that this determination can also be carried out so quickly that their result can be used to control ongoing processes. In addition, sugars are biodegradable and toxicologically safe and do not interfere with the washing process.
Die Menge an Zucker, die der Waschflotte zugesetzt werden muß, hängt in erster Linie von der Empfindlichkeit ab, mit der die ver¬ wendete Verbindung analytisch unter diesen Bedingungen sicher be¬ stimmt werden kann. Selbstverständlich hängt die zu wählende Men¬ ge auch in starken Maße vom Analysenverfahren ab. Bei den erfin¬ dungsgemäß verwendeten reduzierenden Zuckern liegen die Einsatz¬ konzentrationen üblicherweise zwischen etwa 0,02 bis 2 g/1 Wasch¬ lauge, vorzugsweise zwischen etwa 0,1 und etwa 1 g/1 Waschlauge. Werden die reduzierenden Zucker in das Waschmittel, aus dem die Waschlauge hergestellt wird, direkt eingearbeitet, so enthalten diese Waschmittel neben mindestens einem Tensid und mindestens einer Buildersubstanz etwa 1 bis 20 Gew.-%, vorzugsweise 3 bis 10 Gew.-% an reduzierendem Zucker. Wird die Waschlauge nicht aus ei¬ nem Waschmittel, das alle für die Wäsche notwendigen Komponenten enthält, hergestellt, sondern erfolgt die Zubereitung der Lauge durch Zugabe einzelner Wirkstoffe oder Wirkstoffkombinationen, denen der reduzierende Zucker vorher zugesetzt wird, so enthalten diese entsprechend mehr an reduzierendem Zucker.The amount of sugar that must be added to the wash liquor depends primarily on the sensitivity with which the compound used can be determined analytically under these conditions. Of course, the amount to be selected also depends to a large extent on the analytical method. In the reducing sugars used according to the invention, the use concentrations are usually between about 0.02 to 2 g / 1 wash liquor, preferably between about 0.1 and about 1 g / 1 wash liquor. If the reducing sugars are incorporated directly into the detergent from which the wash liquor is produced, these detergents contain, in addition to at least one surfactant and at least one builder substance, about 1 to 20% by weight, preferably 3 to 10% by weight, of reducing sugar . If the wash liquor is not produced from a detergent which contains all the components necessary for washing, the liquor is prepared by adding individual active ingredients or combinations of active ingredients, to which the reducing sugar is added beforehand, they accordingly contain more reducing sugar.
Die analytische Methode, mit deren Hilfe der Gehalt an Zucker in der Waschlauge bestimmt wird, kann in nahezu beliebigen Grenzen frei gewählt und den Bedingungen des Waschverfahrens angepaßt wer¬ den. Bevorzugt werden empfindliche Bestimmungsverfahren, die es erlauben mit geringen Zuckergehalten auszukommen, und solche Ver¬ fahren, die eine schnelle Bestimmung möglichst in kontinuierlicher Weise ermöglichen. Besonders bevorzugt wird deshalb die photome¬ trische Bestimmung des Zuckergehaltes nach einer vorgeschalteten farbbildenden Reaktion zwischen dem Tracer und einem zugesetzten Reagenz. Die farbgebende Reaktion kann dabei jeweils an einzelnen Proben der zu analysierenden Waschlauge durchgeführt werden und führt dann nach Photometrie zu entsprechenden Einzelergebnissen. Für die kontinuierliche Konzentrationsüberwachung bietet sich aber auch die Möglichkeit, die Reaktion zwischen Tracer und Reagenz kontinuierlich in einem aus der Waschlauge abgezweigten Strom durchzuführen, wobei sich das Verfahren der Fließinjektionsanalyse besonders bewährt hat. Bei dieser Methode wird dem abgezweigten Strom der zu analysierenden Lösung, gegebenenfalls nach geeigneter Vorbehandlung, wie Filtration oder Temperierung, ein äquivalenter Strom eines oder mehrerer Reagenzien zudosiert, der gemeinsame Strom dann nach entsprechender Mischung nötigenfalls kontinuier¬ lich weiteren Maßnahmen, wie zum Beispiel Erwärmung, ausgesetzt, bis sich die gewünschte Farbreaktion vollzogen hat und die Lösung einer photometrischen Meßzelle zugeführt werden kann. Typische Flüsse für die Lösungen bewegen sich im Bereich von 0,1 bis 2,5 ml pro Minute. Als Ergebnis wird hier mit einer gewissen Verzögerung ständig ein Meßwert für die gerade vorhandene Tracerkonzentration angezeigt, der es erlaubt, die Konzentration der Lauge kontinuier¬ lich zu verfolgen. Anstelle der vollkontinuierlichen Arbeitsweise kann mit ähnlich gutem Erfolg die periodisch wiederkehrende Be¬ stimmung von Einzelproben mit Hilfe der Fließinjektionsanalyse treten, die ebenfalls vollautomatisch durchgeführt werden kann.The analytical method, with the aid of which the sugar content in the wash liquor is determined, can be freely selected within almost any limits and adapted to the conditions of the washing process. Sensitive determination methods which allow low sugar contents to be used and methods which allow rapid determination in a continuous manner are preferred. The photometric determination of the sugar content after an upstream color-forming reaction between the tracer and an added reagent is therefore particularly preferred. The coloring reaction can be carried out on individual samples of the wash liquor to be analyzed and then leads to corresponding individual results according to photometry. For continuous concentration monitoring, however, there is also the possibility of carrying out the reaction between tracer and reagent continuously in a stream branched off from the wash liquor, the process of flow injection analysis having proven particularly useful. In this method, an equivalent stream of one or more reagents is metered into the branched-off stream of the solution to be analyzed, if appropriate after suitable pretreatment, such as filtration or tempering, and the common stream then, after appropriate mixing, if necessary, further measures such as heating, continuously exposed until the desired color reaction has taken place and the solution can be fed to a photometric measuring cell. Typical flows for the solutions range from 0.1 to 2.5 ml per minute. As a result, with a certain delay, a measured value for the currently existing tracer concentration is continuously displayed, which makes it possible to continuously monitor the concentration of the alkali. Instead of the fully continuous way of working the periodically recurring determination of individual samples can take place with similar good success with the aid of the flow injection analysis, which can also be carried out fully automatically.
Für die erfindungsgemäß als Tracersubstanzen verwendeten reduzie¬ renden Zucker, insbesondere für Glucose, haben sich aromatische Hydrazinverbindungen, beispielsweise 4-Aminobenzhydrazid, als ge¬ eignete farbgebende Reagentien erwiesen. Diese aromatischen Hydra¬ zinverbindungen bilden mit den reduzierenden Zuckern, insbesondere Glucose, intensiv gelb gefärbte Hydrazone, die photometrisch leicht erfaßbar sind. Diese Reaktion ist zum analytischen Nachweis von Zuckern aus der Literatur bekannt, so daß hier auf eine aus¬ führlichere Darstellung der Reaktionsbedingungen verzichtet werden kann. Bemerkenswert ist, daß diese farbgebende Reaktion der Zucker weitestgehend unabhängig von sonstigen Bestandteilen der Wasch¬ mittel abläuft.For the reducing sugars used according to the invention as tracer substances, in particular for glucose, aromatic hydrazine compounds, for example 4-aminobenzhydrazide, have proven to be suitable coloring reagents. These aromatic hydrazine compounds form, together with the reducing sugars, in particular glucose, intensely yellow-colored hydrazones which can be easily detected photometrically. This reaction is known from the literature for the analytical detection of sugars, so that a more detailed description of the reaction conditions can be dispensed with here. It is noteworthy that this coloring reaction of the sugar takes place largely independently of other constituents of the detergent.
Das erfindungsgemäße Verfahren kann mit Vorteil überall dort ein¬ gesetzt werden, wo nachträglich der Gehalt einer Waschlauge an Aktivsubstanz ermittelt werden muß. Dies ist vor allem im gewerb¬ lichen Bereich der Wäscherei der Fall, wo häufig ein und dieselbe Waschlauge für mehrere Waschprozesse verwendet wird und in deren Verlauf durch verschiedene Einflüsse, beispielsweise durch Eintrag von verdünnteren Laugen oder Wasser oder durch Austrag der konzen¬ trierten Lauge mit der Wäsche an Waschaktivsubstanz in unkontrol¬ lierter Weise verarmen kann. Um die Waschlauge wieder auf die Sollkonzentration zu bringen, kann zunächst der aktuelle Gehalt an Aktivsubstanz mit Hilfe der erfindungsgemäßen Methode ermittelt und dann entsprechend dem Ergebnis Waschmittel nachdosiert werden. Da sich das erfindungsgemäße Verfahren weitgehend bis vollständig automatisch durchführen läßt, eignet es sich im besonderen Maße für die mehr oder weniger automatische Steuerung dieser Waschmit¬ teldosierung, die bei der Herstellung oder Regenerierung von Wasch¬ laugen im gewerblichen Wäschereibetrieb heute angestrebt wird. The process according to the invention can advantageously be used wherever the content of active substance in a wash liquor has to be determined subsequently. This is particularly the case in the commercial area of the laundry, where one and the same wash liquor is often used for several washing processes and in the course of which by various influences, for example by adding more dilute liquors or water or by discharging the concentrated liquor the laundry can be depleted of washing active substance in an uncontrolled manner. In order to bring the wash liquor back to the desired concentration, the current content of active substance can first be determined using the method according to the invention and then detergent can be added according to the result. Since the method according to the invention can be carried out largely to completely automatically, it is particularly suitable for the more or less automatic control of this detergent dosing, which is sought today in the production or regeneration of washing liquors in commercial laundries.
B e i s p i e lExample
In einer 13 Kammer-Taktwaschanlage, die kontinuierlich im Gegen- stromverfahren arbeitete, wurde Krankenhauswäsche unter folgenden Bedingungen gewaschen:Hospital laundry was washed in a 13-chamber cycle washing plant, which continuously worked in countercurrent mode, under the following conditions:
Durchlaufzeit: 30 MinutenLead time: 30 minutes
Taktzeit: 138 SekundenCycle time: 138 seconds
Beladung: 35 kg pro KammerLoad: 35 kg per chamber
FlottenVerhältnis: 1:5 Waschmittelkonzen- tration (Soll)Fleet ratio: 1: 5 detergent concentration (target)
- in Kammer 1: 2,8 g/1- in chamber 1: 2.8 g / 1
- in Kammer 5: 1,4 g/1- in chamber 5: 1.4 g / 1
Das verwendete pulverförmige Waschmittel enthielt als Buildersub¬ stanzen Silikat und Soda und als Tenside Alkylbenzolsulfonat, Fettalkoholethoxylat und Seife sowie 5,00 Gew.-% Glucose als Tra¬ cersubstanz. Die Waschmittelkonzentration in der Flotte wurde in Kammer 1 und in Kammer 5 über eine Bypass-Steuerung und die erfin¬ dungsgemäße Analysenmethode erfaßt und durch einen Vergleich der einprogrammierten Soll-Werte mit den gefundenen Ist-Werten mittels eines Mikroprozessors gesteuert.The powder detergent used contained silicate and soda as builder substances and alkylbenzenesulfonate, fatty alcohol ethoxylate and soap as surfactants and 5.00% by weight glucose as tracer substance. The detergent concentration in the liquor was recorded in chamber 1 and in chamber 5 via a bypass control and the analysis method according to the invention and controlled by means of a microprocessor by comparing the programmed target values with the actual values found.
In einem anderen Fall wurde nur an Kammer 5 die automatische Steuerung der Waschmitteldosierung vorgenommen und an Kammer 1 eine konventionelle Zeit-Mengen-abhängige Dosierung verwendet.In another case, the automatic control of the detergent dosing was carried out only in chamber 5 and a conventional time-quantity-dependent dosing was used in chamber 1.
Die zur Analyse verwendete Apparatur war aus Standardbausteinen zusammengesetzt worden, die mit Hilfe von Teflonschläuchen (Innen- durchmesser 0,5 mm) verbunden worden waren. Folgende Lösungen ka¬ men zur Anwendung:The equipment used for the analysis was composed of standard building blocks, which were diameter 0.5 mm) had been connected. The following solutions were used:
Lösung 1: 2,5 g 4-Aminobenzhydrazid und 12 g NaOH in 150 ml Wasser Lösung 2: Käufliche Pufferlösung pH 4,62 (Acetat-Puffer) mit dem gleichen Volumen Wasser verdünntSolution 1: 2.5 g of 4-aminobenzhydrazide and 12 g of NaOH in 150 ml of water Solution 2: Commercial buffer solution pH 4.62 (acetate buffer) diluted with the same volume of water
Beide Lösungen wurden über Pumpen mit 1 ml/Minute getrennt einge¬ speist und über ein T-Stück einer Mischstrecke zugeführt. Vor der Zusammenführung der beiden Lösungen wurden der Lösung 1 mit Hilfe eines Dosierventils und einer Dosierschleife Proben der Wasch¬ flotte (jeweils 20 μl) in segmentierter Form zugeführt. Nach dem Vermischen beider Lösungen wurde der Flüssigkeitsstrom in einer Temperierstrecke auf 70 °C aufgeheizt. Nach Durchlaufen einer Kühlstrecke (20 °C) wurde kontinuierlich die Extinktion der Flüs¬ sigkeit bei 410 Nanometer bestimmt. Die Maximalwerte der Ex¬ tinktion wurden als Maß für die Glucosekonzentration angesehen und als solche kontinuierlich von einem angeschlossenen Rechner ver¬ arbeitet. Die Kalibration erfolgte mit Hilfe von wäßrigen Glu- coselösungen im Konzentrationsbereich zwischen 0,02 und 0,3 g Glucose pro Liter, die mehrmals täglich anstelle der Waschlauge in den Analysenkreislauf eingespeist wurden. Die Korrektur der Em¬ pfindlichkeit erfolgte durch den Rechner automatisch. Eine Kor¬ rektur zur Eliminierung der Eigenextinktion der glucosefreien Waschlauge war im vorliegenden Falle nicht notwendig. Die vom Rechner ermittelten Analysenwerte wurden von einem Mikroprozessor mit den dort einprogrammierten Sollwerten verglichen, der seiner¬ seits die Dosierventile der einzelnen Kammern ansteuerte und ge¬ gebenenfalls eine Nachdosierung des Waschmittels in entsprechender Menge veranlaßte. Both solutions were fed separately via pumps at 1 ml / minute and fed to a mixing section via a T-piece. Before the two solutions were brought together, samples 1 of the washing liquor (in each case 20 .mu.l) were supplied in segmented form to solution 1 using a metering valve and a metering loop. After the two solutions had been mixed, the liquid stream was heated to 70 ° C. in a temperature control section. After passing through a cooling section (20 ° C.), the extinction of the liquid was determined continuously at 410 nanometers. The maximum values of the extinction were regarded as a measure of the glucose concentration and as such were continuously processed by a connected computer. The calibration was carried out with the aid of aqueous glucose solutions in the concentration range between 0.02 and 0.3 g glucose per liter, which were fed into the analysis circuit instead of the wash liquor several times a day. The sensitivity was automatically corrected by the computer. A correction to eliminate the self-extinction of the glucose-free wash liquor was not necessary in the present case. The analysis values determined by the computer were compared by a microprocessor with the target values programmed in there, which in turn actuated the metering valves of the individual chambers and, if necessary, caused the detergent to be replenished in an appropriate amount.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Waschverfahren unter Verwendung einer wäßrigen Lösung von Waschaktivsubstanz, bei dem die Konzentration an Waschaktiv¬ substanz in der Lösung indirekt dadurch ermittelt wird, daß der Gehalt an einem reduzierenden Zucker bestimmt wird, der bei der Zubereitung der Waschlauge in einer Menge zugesetzt wird, die der Menge an Waschaktivsubstanz proportional ist.1. Washing process using an aqueous solution of washing active substance, in which the concentration of washing active substance in the solution is determined indirectly by determining the content of a reducing sugar which is added in the preparation of the washing liquor in an amount which is proportional to the amount of active detergent.
2. Verfahren nach Anspruch 1, bei dem der Zucker in einer be¬ stimmten Menge in dem zur Zubereitung der Waschlauge verwen¬ deten Waschmittel enthalten ist.2. The method according to claim 1, wherein the sugar is contained in a certain amount in the detergent used for the preparation of the wash liquor.
3. Verfahren nach Anspruch 1, bei dem die Bestimmung des Zuk- kergehaltes nach einer farbbildenden Reaktion zwischen dem Zucker und einem der Analysenlösung zugesetzten Reagenz auf photometrischem Wege vorgenommen wird.3. The method according to claim 1, wherein the determination of the sugar content is carried out after a color-forming reaction between the sugar and a reagent added to the analysis solution by photometric means.
4. Verfahren nach Anspruch 3, bei dem die Bestimmung des Zucker¬ gehaltes kontinuierlich in einem aus der Waschlauge abge¬ zweigten Strom mit Hilfe der Fließinjektionsanalyse vorgenom¬ men wird.4. The method according to claim 3, in which the determination of the sugar content is carried out continuously in a stream branched off from the wash liquor with the aid of the flow injection analysis.
5. Verfahren nach Anspruch 4, bei dem als farbbildendes Reagenz ein aromatisches Hydrazinderivat verwendet wird.5. The method according to claim 4, in which an aromatic hydrazine derivative is used as the color-forming reagent.
6. Verfahren nach Anspruch 5, bei dem als Reager.z 4-Aminobenzhy- drazid eingesetzt wird. 6. The method according to claim 5, in which 4-Aminobenzhy- drazid is used as Reager.z.
7. Waschverfahren nach einem der Ansprüche 1 bis 6, bei dem das Ergebnis der Gehaltsbestimmung in einem teil- oder vollauto¬ matisierten Prozeß zur Steuerung der Waschmitteldosierung bei der Herstellung oder Regenerierung der Waschlauge verwendet wird.7. Washing method according to one of claims 1 to 6, in which the result of the content determination is used in a partially or fully automated process for controlling the detergent dosage in the production or regeneration of the wash liquor.
8. Verwendung von reduzierendem Zucker in Waschmittel als Tra¬ cersubstanz für die Ermittlung der Wasch ittelkonzentration in einer aus diesem Waschmittel hergestelltem Lauge. 8. Use of reducing sugar in detergent as a tracer substance for determining the detergent concentration in an alkali produced from this detergent.
PCT/EP1993/002170 1992-08-24 1993-08-16 Washing process WO1994004741A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US08/392,757 US5498546A (en) 1992-08-24 1993-08-16 Washing process
JP6505885A JPH08500439A (en) 1992-08-24 1993-08-16 Cleaning method
EP93919061A EP0656081B1 (en) 1992-08-24 1993-08-16 Washing process
DE59304835T DE59304835D1 (en) 1992-08-24 1993-08-16 WASHING PROCEDURE

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4228021.4 1992-08-24
DE4228021A DE4228021A1 (en) 1992-08-24 1992-08-24 washing method

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AU735416B2 (en) * 1996-11-06 2001-07-05 Sequenom, Inc. Dna diagnostics based on mass spectrometry
US6361960B1 (en) * 1999-11-09 2002-03-26 Environmentally Sensitive Solutions, Inc. Method and test kit for measuring concentration of a cleaning agent in a wash liquor
US7282101B2 (en) * 2003-08-19 2007-10-16 Mccurdy Brent K Method for dissolving a solid material in a liquid
CA3110505A1 (en) 2018-08-27 2020-03-05 Ecolab Usa Inc. System and technique for extracting particulate-containing liquid samples without filtration

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DE2949254A1 (en) * 1979-12-07 1981-06-25 Licentia Patent-Verwaltungs-Gmbh, 6000 Frankfurt Automatic control of detergent concn. in washing machines - by photoelectric monitoring of fluorescent components in wash liquor
WO1992009568A1 (en) * 1990-12-03 1992-06-11 Monash University Fluorescence labelling reagent and use therefor

Also Published As

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US5498546A (en) 1996-03-12
EP0656081A1 (en) 1995-06-07
DE4228021A1 (en) 1994-03-03
DE59304835D1 (en) 1997-01-30
EP0656081B1 (en) 1996-12-18
JPH08500439A (en) 1996-01-16

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